Abstract
A novel zeolite imidazole framework@hydroxyapatite composite (ZIF-8@HAP) was constructed via in-situ growth and developed for efficient dispersive solid-phase extraction (DSPE) of three benzodiazepines from urine samples. The prepared composite was characterized by scanning electron microscopy, energy-dispersive spectrometer, Fourier-transform infrared spectrometry, X-ray diffractometry, zeta potential analyzer, and nitrogen adsorption-desorption experiment. Characterization results showed typical dodecahedron ZIF-8 crystals that were uniformly located on the surface of rod-like HAP. The combination of ZIF-8 and HAP made the surface area significantly enhanced from 4.68 to 205.44 m2 g−1. Compared with a commercial C18 adsorbent, ZIF-8@HAP exhibited superior removal performance for interfering components from urine and offered better extraction properties for the analytes. The prepared ZIF-8@HAP was applied as an adsorbent in DSPE, and the main experimental parameters, including pH and ionic strength of solution, adsorbent amount, adsorption time, elution solvent, and volume, were investigated. Under optimal conditions, the adsorption for 250 ng mL−1 of each analyte in 4 mL of urine was accomplished within 2 min using 60 mg of adsorbent. The method of ZIF-8@HAP–based DSPE followed by high-performance liquid chromatography gave enhancement factors of 13.3–15.3, linear ranges of 2.5–500 ng mL−1, and limits of detection (S/N = 3) of 0.7–1.4 ng mL−1. The relative recoveries at three spiked levels ranged from 88.7 - 102% with intra-day and inter-day precisions from 3.0 - 10.3% and 2.3 - 12.3%, respectively. These results indicated that the proposed strategy had promising applicability for convenient, rapid, and efficient determination of benzodiazepines in urine samples.
Graphical abstract

In-situ fabrication of ZIF-8@HAP composite for dispersive solid-phase extraction of benzodiazepines in urine samples.



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This study was supported by the Research Foundation of Education Bureau of Hebei Province, China (grant number ZD2018014), the Training Foundation of North China University of Science and Technology, China (grant number JQ201717), and the Graduate Student Innovation Fund of Hebei Province, China (grant number JXC2019004).
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Conceptualization: Zi-Ling Li. Methodology: Zi-Ling Li and Zi-Yang Zhang. Validation: Chun-Yan Meng. Data curation: Zi-Ling Li and Teng-Wen Zhao. Writing—original draft: Zi-Ling Li and Man-Man Wang. Writing—review and editing: Man-Man Wang. Software: Zi-Yang Zhang. Investigation: Qian-Ying Zhang. Funding acquisition: Man-Man Wang.
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Li, ZL., Zhang, ZY., Zhao, TW. et al. In-situ fabrication of zeolite imidazole framework@hydroxyapatite composite for dispersive solid-phase extraction of benzodiazepines and their determination with high-performance liquid chromatography-VWD detection. Microchim Acta 187, 540 (2020). https://doi.org/10.1007/s00604-020-04517-y
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DOI: https://doi.org/10.1007/s00604-020-04517-y